O-(1 - alkoxycarbonyl-1-propen-2-yl)-phosphorodihalidates and -phosphorodihalothionates

ABSTRACT

0-(1-ALKOXYCARBONYL-1-PROPEN-2-YL)-PHOSPHORODIHALIDATES AND -PHOSPHORODIHALOTHINATES USEFUL AS INTERMEDIATES IN THE PRODUCTION OF INSECTICIDES-ACARICIDES.

United States Patent 0-(1 ALKOXYCARBONYL-1-PROPEN-2-YL)-PHOS-PHORODIHALIDATES AND -PHOSPHORODI- HALOTHIONATES Jean Pierre Leber andKarl Lutz, Basel, Switzerland, assignors to Sandoz Ltd. (also known asSandoz AG), Basel, Switzerland No Drawing. Continuation-impart ofapplication Ser. No. 838,663, July 2, 1969. This application Nov. 12,1969,

' Ser. No. 876,087

Claims priority, application Switzerland, July 15, 1968,

10,551/68; Nov. 16, 1968, 17,054/68 Int. Cl. C07f 9/14; A01n 9/36 US.Cl. 260-941 25 Claims ABSTRACT OF THE DISCLOSURE O (1alkoxycarbonyl-l-propen-Z-yl)-phosphorodi halidates and-phosphorodihalothionates useful as intermediates in the production ofinsecticides/acaricides.

This application is a continuation in part of application No. 838,663filed July 2, 1969, now abandoned.

The present invention relates to new organic phosphorus halides.

According to our invention we provide compounds of Formula I,

in which R signifies an alkyl radical of 1 to carbon atoms,

X signifies a hydrogen, chlorine or bromine atom,

the Ys, which are the same, each signify a chlorine or bromine atom, andZ signifies an oxygen or a sulphur atom.

According to our invention we also provide a process for the productionof a compound of Formula I, which comprises reacting a phosphoric oxyorthio-chloride or bromide with a compound of Formula II,

CH COCHXCOOR II in which X and R are as defined above, in the presenceof an acid acceptor, or with a salt of a compound of Formula II.

The salt of compound of Formula II is preferably an alkali metal salt.

The reaction may be carried out without solvent or in the presence of asolvent which is inert under the reaction conditions, for example anaromatic hydrocarbon, e.g. toluene or xylene, a halogenated hydrocarbon,e.g. chloroform or trichloroethylene, or an ether, e.g. dioxane. Theacid acceptor may be an organic base, for example triethylamine, or aninorganic base, for example sodium bicarbonate. The reaction may becarried out at a temperature of about 10 to +50 C., preferably at 10 C.to room temperature. When a salt of a compound of Formula II is used inplace of the compound of Formula II, it is not necessary to use an acidacceptor. It is preferred to use substantially equimolar proportions ofthe phosphorus halide, of the compound of Formula II or of the salt ofthe compound of Formula II and, if an acid acceptor is used, of the acidacceptor. The reaction is preferably carried out by stirring thereaction mixture for about half an hour at a temperature between 10 and+50 C., preferably at -10 to +10 C., and then for about minutes at roomtemperature. The reaction mix- 3,634,556 Patented Jan. 11, 1972 ture isthen washed, optionally after the addition of a solvent when thereaction is elfected without solvent, and, after drying, the solvent isremoved at a bath temperature of about 20 to 50 C. in a vacuum. Theliquid residue may be distilled in a high vacuum to obtain the purecompound of Formula I as an oil.

The preferred compounds of Formula I are those in which X signifies ahydrogen or chlorine atom.

The compounds of Formula I obtained in accordance with the process ofthe invention predominantly have a cis configuration in the crotonicacid radical (i.e. the -CH group is cis to the --COOR group) when anorganic base, e.g. triethylamine, is used as acid acceptor. When, forexample, sodium bicarbonate is used as acid acceptor, the portion of cisconfiguration in the crotonic acid radical of the compound of Formula Iis smaller than when triethylamine is used. When, for example, a sodiumacetoacetic acid ester is used in place of the acetoacetic ester ofFormula II and an acid acceptor, then compounds of Formula Ipredominantly having the trans form in the crotonic acid radical areobtained. The stereoisomeric composition of the compounds of Formula Imay be determined in conventional manner by the nuclear magneticresonance spectrum.

The compounds of Formula I obtained in accordance with the process ofthe invention are useful as intermediates for the production ofbiocides, e.g. insecticides and acaricides. For example, the compoundsof Formula I react with a corresponding amount of an alkanol, in thepresence of an acid acceptor to yield compounds on which both thehalogen atoms Y on the phosphorus atom have been exchanged for alkoxyradicals. The halogen atoms Y on the phosphorus atom may also beexchanged for two different alkoxy radicals in two separate stages. Inthe first stage about 1 mol of an alkanol is reacted with a compound ofFormula I in the presence of, a preferably equimolar amount of, an acidacceptor and the resulting compound is then reacted in the second stagewith about 1 mol of a different alkanol, again in the presence of, apreferably equivalent amount of, an acid acceptor.

By the processes described immediately above, it is possible to obtainbiocides, e.g. insecticides and acaricides, some of which biocides areknown and may be used in known manner. Those of the biocides which arenot specifically known can be used in the same manner as the knownbiocides.

The invention is illustrated, but in no way limited by the followingexamples in which the temperatures are in degrees centigrade.

EXAMPLE 1 Y O- l-ethoxycarbonyll-propen-Z-yl) phosphordichloridate g. (1mol) of acetoacetic acid ethyl ester and 101 g. (1 mol) of triethylamineare added over a period of half an hour to 154 g. (1 mol) of phosphorusoxychloride in 500 cc. of toluene with stirring and at a temperature ofl0, whereby triethylamine hydrochloride precipitates. The reactionmixture is subsequently stirred for a further half hour at a temperaturebetween 10 and +10 and then for 15 minutes at 20. The resultingprecipitate is subsequently filtered oil? and the solvent in thefiltrate is removed at a bath temperature of 50 in a water jet vacuum toyield crude O-(l-ethoxycarbonyll-propen-Z-yl) phosphorodichloridate. Thepure compound has a B.P. of 77-78/0.15 mm. of Hg and has a refractiveindex of n =l.4700.

Analysis.C H Cl O P; molecular weight: 247.01 Calc. (percent): C, 29.2;H, 3.7; Cl, 28.7. Found (percent): C, 29.8; H, 3.7; Cl, 29.4.

3 EXAMPLE 2 O-( l-ethoxycarbonyl-1-propen-2-yl) phosphorodichloridate11.5 g. of sodium metal are pulverized in 1.2 liters of toluene at about110 with a vibro mixer. 65 g. of acetoacetic acid ethyl ester are thenadded dropwise to the sodium suspension at 2040. After the reaction iscompleted the viscous suspension of sodium acetoacetic acid ethyl esteris added dropwise to a solution of 77 g. of phosphorus oxychloride in100 cc. of toluene at -20. The reaction mixture is subsequently stirredat room temperature for half an hour and the toluene is then distilledoff in a vacuum. The residue is taken up in ether, the precipitatedsodium chloride is filtered off and the filtrate concentrated byevaporation. The resulting pure compound has a B.P. of 4850/1O mm. ofHg. It consists almost exclusively of O-(l-ethoxycarbonyl-1-propen-2-yl) 'phosphorodichloridate having the trans form in the crotonic acidradical.

EXAMPLE 3 O-( l-methoxycarbonyl-l-propen-Z-yl) thiophosphorodichloridate50.5 g. (0.5 mol) of triethylamine are added with stirring over a periodof 30 minutes and at a temperature of 10 to a mixture of 84.5 g. (0.5mol) of phosphorus thiochloride and 58 g. (0.5 mol) of acetoacetic acidmethyl ester, whereby triethylamine hydrochloride precipitates. Thereaction mixture is subsequently stirred for a further half hour at atemperature between -10 at 10-20. The reaction mixture is subsequentlystirred at room temperature for minutes, is washed with ice water andafter drying with sodium sulphate the toluene is distilled off in avacuum. The residue is distilled yielding O-(l-methoxycarbonyl 1propen-Z-yl) thiophosphorodichloridate having a B.P. of "/10- mm. of Hg.The compound exclusively consists of the trans form in the crotonic acidradical.

EXAMPLE 5 O- 1-chloro-l-methoxycarbonyl- 1-propen-2-yl)phosphorodichloridothionate 30.5 g. (0.3 mol) of triethylamine' areadded at 10 with stirring and over a period of 1 hour to a mixture of 51g. (0.3 mol) of phosphorus thiochloride and g. (0.3 mol) ofot-chloro-acetoacetic acid methyl ester in 100 cc. of toluene. Stirringis subsequently continued at room temperature for about half an hour.The reaction mixture is then washed twice With ice water, the toluenelayer is separated, dried with sodium sulphate and the toluene isdistilled off. Crude O-(l chloro-lmethoxycarbonyl 1-propen-3-yl)phosphorodichloridothionate is obtained. The pure compound has a B.P. of45-48/5.10 mm. of Hg. The relationship cisztrans isomer in the crotonicacid radical is 9:1.

Analysis.C HgCl O PS; molecular weight: 283.5. Calc. (percent): C, 21.2;C1, 37.5; P, 10.9; S, 11.3. Found (percent): C, 21.2; C1, 36.8; P, 11.1;S, 11.0.

The following compounds of Formula I are obtained in a manner analogousto that described in Examples 1, 3 and 5.

Analysis, percent;

Relationship Moleccisztrans in Found Calculated Empirical ularB.P./n1m.of Hg, the crotonic Example R X Y Z formula weight C. acidradical 0 01 P S C 01 P S 01 0 0 11 012011? 232.99 65/0.01 9:1 26.3 30.813.4 5.8 01 o C1H Cl2O1P 261.04 9: 32.4 26.5 11.9 2.2 Cl 0 oeHnclzorP275.07 85:15 34.1 24.9 11.2 4.9 11. 01 o 061415615041 289.09 85:15 36.823.9 10.8 7.4 c1 0 05118014011 281.46 9:1 26.4 36.9 10.9 25.6 c1 0011110014011 295.49 911 28.9 35.8 10.4 ..28.5 C1 8 ofimonosrs 263.00 9:127.7 26.8 11.9 12.5 27.3 27.0 11.8 12.2 01 s C H11ClzOaPS 277 45/1-1095:5 30.8 24.8 10.9 11.7 30.2 25.6 11.2 11.6 01 s o Hnc1 o3Ps 277 431-10- 95:5 30.7 25.1 10.8 11.7 30.2 25.6 11.2 11.6 Cl 8 CsHraClzOzPS 29153/1-10 85:15 33.4 24.1 10.3 10.8 33.0 24.4 10.7 11.0 C1 8 C HraClzOaPS291 54"/1-10 9:1 33.5 23.8 10.1 10.9 33.0 24.4 10.7 11.0 01 sC3H13C11O3PS 291 5271-10- 9:1 33.3 24.0 9.8 10.8 33.0 24.4 10.7 11.0 01s C8H13ClzO3PS 291 40--45/mo1. dist. 95:5 33.1 23.7 10.1 11.0 33.0 24.410.7 11.0

(finger temp.) Cl 8 (39111501203198 305 6870/1-10- 85:15 36.3 23.2 9.910.9 35.4 23.3 10.2 10.5 01 s CDHLSClzOSPS 305 4550/m0l. dist. 9:1 35.824.0 9.9 10.8 35.4 23.3 10.2 10.5

(finger temp.) 01 s otflronoals 297.5 55-53/10 9:1 24.8 35.3 10.5 10.224.2 35.8 10.8 10.4 01 s C1HmCl O3PS 311.5 62/5-10- 9:1 27.7 33.8 10.39.8 27.0 34.2 10.3 9.3 Cl S C1HmCl3O PS 311. 52/10 85:15 27.5 33.3 9.99.7 27.0 34.2 10.3 9.3 or 8 681112013031 8 325.5 62-64/10- 9:1 30.1 32.29.2 8.9 29.5 32.7 9.8 9.5 11052111.--- C1 C1 S CvHiiClaOaPS 339.573-75/10 9:1 32.8 30.7 8.6 8.9 31.9 31.4 9.1 9.4

and +10", and then for 15 minutes at 20. 250 cc. of What is claimed is:chloroform are then added to the reaction mixture, the 5 1. Compounds offormula: mixture is washed, dried and the solvent removed in a Y Z waterjet vacuum at a bath temperature of 50. Crude uO-(l-methoxycarbonyl-l-propen 2-yl) thiophosphorodi- /POC=CXCOOR Ichloridate is obtained. The pure compound has a B.P. of Y CH3 0 42 /5.10mm. of Hg. The relationship c1s.trans isomer 60 m Whlch R slgmfies alkylof 1 to 5 Carbon atoms X in the crotonic acid radical is about 9: 1.

Analysis.--C H Cl O PS; molecular weight: 249. Calc. (percent): C, 24.1;C1, 28.4; P, 12.4; S, 12.8. Found (percent): C, 24.4; C1, 28.4; P, 12.1;S, 12.8.

EXAMPLE 4 nifies hydrogen, chlorine or bromine, the Ys, which are thesame, each signify chlorine or bromine, and Z signifies oxygen orsulphur.

2. A compound as claimed in claim 1, wherein R signifies ethyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies oxygen.

3. A compound as claimed in claim 1, wherein R signifies methyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies sulphur.

4. A compound as claimed in claim 1, wherein R signifies methyl, Xsignifies chlorine, Y signifies chlorine and Z signifies oxygen.

5. A compound as claimed in claim 1, wherein R signifies methyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies oxygen.

6. A compound as claimed in claim 1, wherein R signifies isopropyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies oxygen.

7. A compound as claimed in claim 1, wherein R signifies tert. butyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies oxygen.

8. A compound as claimed in claim 1, wherein R signifies tert. pentyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies oxygen.

9. A compound as claimed in claim 1, wherein R signifies ethyl, Xsignifies chlorine, Y signifies chlorine and Z signifies oxygen.

10. A compound as claimed in claim 1, wherein R signifies n-propyl, Xsignifies chlorine, Y signifies chlorine and Z signifies oxygen.

11. A compound as claimed in claim 1, wherein R signifies ethyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies sulphur.

12. A compound as claimed in claim 1, wherein R signifies n-propyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies sulphur.

13. A compound as claimed in claim 1, wherein R signifies isopropyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies sulphur.

14. A compound as claimed in claim 1, wherein R signifies n-butyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies sulphur.

15. A compound as claimed in claim 1, wherein R signifies isobutyl, Xsignifieshydrogen, Y signifies chlorine and Z signifies sulphur.

16. A compound as claimed in claim 1, wherein R signifies sec-butyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies sulphur.

17. A compound as claimed in claim 1, wherein R signifies tert. butyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies sulphur.

18. A compound as claimed in claim 1, wherein R signifies isopentyl, Xsignifies hydrogen, Y signifies chlorine and Z signifies sulphur.

19. A compound as claimed in claim 1, wherein R signifies tert. pentyl,X signifies hydrogen, Y signifies chlorine and Z signifies sulphur.

20. A compound as claimed in claim 1, wherein R signifies ethyl, Xsignifies chlorine, Y signifies chlorine and Z signifies sulphur.

21. A compound as claimed in claim 1, wherein R signifies n-propyl, Xsignifies chlorine, Y signifies chlorine and Z signifies sulphur.

22. A compound as claimed in claim 1, wherein R signifies isopropyl, Xsignifies chlorine, Y signifies chlorine and Z signifies sulphur.

23. A compound as claimed in claim 1, wherein R signifies n-butyl, Xsignifies chlorine, Y signifies chlorine and Z signifies sulphur.

24. A compound as claimed in claim 1, wherein R signifies n-pentyl, Xsignifies chlorine, Y signifies chlorine and Z signifies sulphur.

25. A compound as claimed in claim 1, wherein the CH is cis to the COORin the crotonic acid radical.

No references cited.

CHARLES B. PARKER, Primary Examiner A. M. SUTTO, Assistant Examiner U.S.Cl. X.R.

